Functionally ended polymers

Fig. 2. Functional end groups and solution viscosity during polyester resin manufacture. Acid value is defined as the milligrams of KOH required to neutralize 1 g of polymer hydroxyl value is defined as the milligrams of acid equivalent required to neutralize 1 g of polymer. Solution viscosities are...

Grafting reactions alter the physical and mechanical properties of the polymer used as a substrate. Grafting differs from normal chemical modification (e.g., functionalization of polymers) in the possibility of tailoring material properties to a specific end use. For example, cellulose derivatization improves various properties of the original cellulose, but these derivatives cannot compete with many of the petrochemically derived synthetic polymers. Thus, in order to provide a better market position for cellulose derivatives, there is little doubt that further chemical modification is required. Accordingly, grafting of vinyl monomers onto cellulose or cellulose derivatives may improve the intrinsic properties of these polymers. 

Two methods for cleaving the nitroxide functionality from polymers made by NMP are summarized in Table 9.23. Transfer agents such as thiols " ordithiuram disulfides (Scheme 9.50) can be used for end group replacement and lead to the... 

Allyl56), vinylsilane62), acyl lactam63 , phosphonic ester64 , and many other functions have been attached to chain ends. Polymers fitted with dyes53) or fluorescent groups65) have been made in good yields. 

A thick is deposited on top. This is then covered with a molecularly thin film of lubricant to minimize wear during start-stop contacts and to passivate the disc surface against contamination and corrosion. High-molecular-weight perfluoropolyalkylether (PFPE) polymers are widely used for this purpose. In order to improve surface bonding, the PFPEs are modified with specific functional end groups. All these molecules have similar backbone structures, namely ... 

The procedure described here is not limited to the preparation of polymers such as 2. Starting from the difunctional silane 3 we have synthesized a copolymer, poly(dimethyl-co-isocyanopropylmethyl-siloxane) > as well as a linear homopolymer, poly(isocyanopropyl-methylsiloxane) 8 (Scheme 2). Indeed, preparation of a monofunctional analogue of 2. and h creates the potential for end-capping with an isocyanide function any polymer containing other functional groups, thereby in principle permitting mixed ligand complexes of polymers to be accessed. 

Reactive impact modifiers are preferred for toughening of PET since these form a stable dispersed phase by grafting to the PET matrix. Non-reactive elastomers can be dispersed into PET by intensive compounding but may coalesce downstream in the compounder. Reactive impact modifiers have functionalized end groups. Functionalization serves two purposes - first, to bond the impact modifier to the polymer matrix, and secondly to modify the interfacial energy between the polymer matrix and the impact modifier for enhanced dispersion. Some examples of commercially available reactive impact modifiers for PET are shown in Table 14.3. An example of a non-reactive elastomer that can be used in combination with reactive impact modifiers is ethylene methyl acrylate (EMA), such as the Optema EMA range of ethylene methyl acrylates manufactured by the Exxon-Mobil Chemical Company (see Section 4.2). 

The alkyllithium-initiated, anionic polymerization of vinyl and diene monomers can often be performed without the incursion of spontaneous termination or chain transfer reactions (1). The non-terminating nature of these reactions has provided methods for the synthesis of polymers with predictable molecular weights and narrow molecular weight distributions (2). In addition, these polymerizations generate polymer chains with stable, carbanionic chain ends which, in principle, can be converted into a diverse array of functional end groups using the rich and varied chemistry of organolithium compounds (3). 

The application of these functionalization reactions to polymers has been catalogued in the anionic polymer review literature (4-6). Unfortunately, many of the reported applications of these functionalization reactions to anionic chain-ended polymers have not been well characterized (7). In order to exploit these functionalization reactions to their potential, well-defined procedures for quantitative chain end functionalization must be available. 

Fig. 9.19 Preparation of polymer brushes on solid surfaces by a) chemical grafting of end-functionalized linear polymers or selective adsorption of asymmetric block copolymers and b) by surface-initiated polymerization (SIP) using initiator functions on the solid surface. The depicted SAM bearing to-functionalities...

The prepolymers described above are one type of telechelic polymer. A telechelic polymer is one containing one or more functional end groups that have the capacity for selective reaction to form bonds with another molecule. The functionality of a telechelic polymer or prepolymer is equal to the number of such end groups. The macrodiol and macrodiisocyanate telechelic prepolymers have functionalities of 2. Many other telechelic prepolymers were discussed in Sec. 2-12. (The term functional polymer has also been used to describe a polymer with one or more functional end groups.)... 

Some ring-opening polymerizations proceed by a different route called activated monomer (AM) polymerization, which typically involves a cationic or anionic species derived from the monomer. For example, cationic AM polymerization proceeds not with monomer, but with protonated monomer that reacts with the neutral functional end group of the propagating polymer... 

Most of the methods for synthesizing block copolymers were described previously. Block copolymers are obtained by step copolymerization of polymers with functional end groups capable of reacting with each other (Sec. 2-13c-2). Sequential polymerization methods by living radical, anionic, cationic, and group transfer propagation were described in Secs. 3-15b-4, 5-4a, and 7-12e. The use of telechelic polymers, coupling and transformations reactions were described in Secs. 5-4b, 5-4c, and 5-4d. A few methods not previously described are considered here. 

Both monomer and polymer molecules with suitable functional end groups can react. 

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